Non-yellowing softening agent for cotton and rayon textiles

ABSTRACT

Process for producing a novel composition of the class normally employed as softening agents for cotton and rayon textiles during hot finishing treatments, and storage of the composition. More particularly, the invention relates to the alkali metal salts of sulfonated bisfumarates of the mixed glycerides of unsaturated fatty acids, having at least 15 percent by weight of polyunsaturated fatty acids therein.

United States Patent Brown 51 July 25, 1972 NON-YELLOWING SOFTENING AGENT [56] References Cited T FOR COT ON AND RAYON TEXTILES UNITED STATES PATENTS 72 t M l t 1 m James Bmwn Char N C 2,734,833 2/1956 Thurston ..1 l7/l39.5 [73] Assignee: American Cyanamid Company, Stamford,

rIn- Primary Examiner-Elbert L. Roberts [22] Filed: March 12 1970 Attorney-Charles .l. Fickey [21] Appl. No.: 19,066 [57] ABSTRACT Reh'ed s Applicmion Data Process for producing a novel composition of the class normally employed as softening agents for cotton and rayon texcomlnuatlon-m'pafl of 576,349, P tiles during hot finishing treatments, and storage of the com- ]966: abandonedposition. More particularly, the invention relates to the alkali metal salts of sulfonated bisfumarates of the mixed glycerides [52] US. Cl ..260/400, 252/8.7, l 17/] 39.5 f unsaturated fzmy acids, having at least 5 percent by weight [51] Int. Cl. ..C07c 143/90, Cl ld 1/28 f polyunsaturated f t acids therein [58] Field of Search ..260/400 3 Claims, No Drawings NON-YELLOWING SOFTENING AGENT FOR COTTON substrates such as toweling, for example, unless a surface ac- AND RAYON TEXTILES tive agent which imparts rewettability were added to the prior art softening agent, however, this substantially reduced the This application is a continuation-in-part of co-pending aphandle imparted by the softening agent. plication, Ser. No. 576,849, filed Sept. 2, 1966 now aban- 5 It is an object of this invention to obtain a softening agent doned. for cotton and rayon textiles and blends thereof having high This invention relates to a novel process for producing a quality handle and having good rewettability. novel composition of the class normally employed assoitening Another object is to obtain a softening agent which is a agents for cotton and rayon textiles during hot finishing treatliquid. ments, and storage of the composition. More particularly, the Another object is to obtain a softener agent which is cold invention relates to the alkali metal and ammonium salts of water soluble.

bis-esters of sulfosuccinic acid and glycerides of hydroxy-con- Another object is to provide a process for producing said taining, unsaturated higher fatty acids. The invention also re- Product which Pt i more econ mical as a result of fewer lates to cellulosic and cellulosic containing substrates, such as ritical steps, temperatures, and reaction times required. toweling, having a high affinity for water, i.e., good rewetta- Another object is to obtain a finishing agent composition bility, after impregnating with the novel softening composiwhich when employed on textile cellulosic material such as tion. cotton and rayon textiles does not impart an undesirable yel- Prior compositions and process of making those composilowing of the fabric subsequent to the finishing thereof. tions, such as typically disclosed in U. S. Pat. No. 2,734,833, O her objects become apparent from the above and follow- (I) require fatty acid radicals to be derived from animal and ing disclosure. vegetable oils and fats with no substantial amounts of hydroxy The objects of this invention are obtained by a novel comacids and having less than 15 percent by weight of polyunsatuposition described below, the process of making the composirated fatty acids therein, or in which the unsaturation is tion, and cellulosics impregnated with the composition.

reduced to below the 15 percent, and (2) require heat treat- The novel composition 'of this invention comprises a metal ment of the monoglyceride in the presence of at least 10 mole rammonium salt of a sulfosuccinate-type bis-ester of a percent of added fatty acid such as stearic acid, palmitic acid, onoglyooride of a hydroxy-containing, unsaturated higher oleic acid, etc., to prevent the formation of insoluble resins bef tty id, Th bis-ester i b li d t hav the f llowi lieved to be cross-linked glycerol-fumaric (or glycerolmaleic) e tr tural f rmula;

esters. Thus, prior art processes fall within specific limitations wherein R is a ricinoleoyl group, R is hydrogen or lower alkyl, as to the nature of the fatty acid which may be employed, and M is an ammonium or alkali metal cation, (e.g., sodium, potasrequire specific process limitations such as those described sium, etc.) and n and n, are each an integer from 0 to 2, above, in order to obtain a satisfactory product. Moreover, the 40 where the sum of n and n, is at least 1 to about 3.

products of the prior art processes, such as those discussed The term hydroxy-containing, unsaturated higher fatty above, are Softeners which. n ppli o cellulosic or celacid" includes acids such as ricinoleic acid and substituted lulosic-containing substrates such as textile materials, provide forms thereof, provided the acids are the functional equivalent a final P which has a reduced affihhy water, iof ricinoleic acid in the composition of this invention. The which does not have good l"wllemihihtyfatty acid contains at least one hydroxy group. The preferred In addition to the above limitations of prior processes, it f tt acidisricinoleic m should be noted that the prior art processes were expensive A typical composition is the sulfosuccinate f the because of a large number of Steps required the higher monoglyceride of ricinoleic acid, of the following formula:

peratures required, and the long periods of reaction required, The major commercially available ricinoleic acid-containor combinations of these. In the prior processes, if anY of the ing oil is castor oil which normally contains at least about 75 Steps Wcrc eliminated, temperatures times of reaction percent ricinoleic acid, and preferably at least about 80 perwere significantly modified, the problem of increased degrees cent, a typical castor oil composition being: of formation of undesirable cross-linked polymers became more pronounced. Moreover, if cross-linking was avoided, the ricimleic acid 85% final softening agent product characteristically required hot oleic id 8.5% water in order to obtain solubility, and the softening agent linoleic acid 3.5% product itself characteristically was in the form of a solid. swam 05-10% Both the property of being solid, and the property of being dihydmxysteafic acid 1- 2% soluble only in hot water increased the expense of handling I and of employing the softening agents in subsequent use on a h be holed h 011 f y readily and textile substrate. Additionally, the use of the prior art softenm l lly available ll which contains a hydroxy fatty acid" ing agents on cellulosic or cellulosic containing materials as a major component It is believed that y an unsaturated, resulted in a loss of afiinity for water. Therefore, the prior art hydroxy acid of this type provides the beneficial results of this softening agents were characteristically limited to uses which invention.

did not require good rewettability. Accordingly the prior art The process of preparing the compositions of this invention softening agents characteristically could not be employed on 7 may be defined as reacting a monoglyceride of a hydroxy-containing, unsaturated higher fatty acid with an unsaturated dibasic aliphatic carboxylic acid or anhydride of the fumaricacid-type in an amount sufficient to form a bis-ester of said monoglyceride, and sulfonating said bis-ester.

Although the fumaric-type-acid may be any one or more of the fumaric acid series, fumaric acid is the preferred acid to be reacted with the monoglyceride. Other suitable dibasic unsaturated acids include maleic, citraconic, mesaconic, pyrocinchonic, glutaconic, hydromuconic, and the like.

Although it is not essential that the bis-ester referred to above in the process of this invention be the reaction product resulting from the use of 100 percent pure monoglyceride, the preferred embodiment employs glycerides which are substantially solely the monoglycerides, such as would be obtained by transesterifying a triglyceride of ricinoleic acid, i.e., castor oil, with glycerine in the presence of a catalytic amOunt of a hydroxide of an alkali metal, employing the triglyceride and the glycerine in relative ratio of from about 1:4 up to about 3:4. However, a mixture of monoglycerides and diglycerides is normally present in the product of such a transesterification, and such a mixture has been found to contain a molar ratio of these two constituents within the range of about 50-95 percent of monoglyceride and about 50-5 percent of diglyceride. It is within the scope of this invention to employ such a mixture.

characteristically, the ricinoleic acid (the primary component of castor oil) bis-ester is prepared by a two or three step process. Ifthe monoglyceride is already available, it is not necessary to go through the first step. However, the monoglyceride is preferably obtained by the process described in the preceding paragraph. In that process, typical hydroxides include sodium hydroxide, ammonium hydroxide, etc. After a reaction sufficient to form the monoglyceride product, the monoglyceride and unsaturated acid or acid anhydride of the fumaric-acid-type are admixed and condensed sufficiently to obtain a fumaric-acid-type bis-ester. The fumaric-acid-type acid or anhydride may be any acid or acid-anhydride of an acid of the fumaric-acid series including, for example, maleic acid, glutaconic acid, citraconic acid, mesaconic acid, hydromuconic acid, pyrocinchonic acid, and the like. Preferably, the fumaric-acid-type compound is employed in an amount of at least about one-half mole of fumaric-type acid per mole of the glycerides. The resulting bis-ester is then sulfonated in a conventional manner by refluxing, normally under pressure, in the presence of an aqueous solution of alkaline metal or ammonium bisulfite or metabisulfite whereby the corresponding salt is obtained directly. Also, preferably the sulfonating reaction is carried out in the presence of an alcohol such as isopropyl alcohol.

Salts of other bases may be readily obtained by first acidifying an alcoholic solution of the alkali metal or ammonium salts whereby the free sulfonic acid is obtained, filtering off the inorganic salt of the acid used and reacting the sulfonic acid with the desired base. Although they are not ordinarily employed in textile finishing treatments, salts of the polyvalent metals such as calcium, barium, zinc, lead, cadmium, and the like may be prepared, if desired, by adding stoichiometric quantities of their oxides or hydroxides to the alcoholic sulfosuccinic acid ester solution followed by stirring until the salt formation is complete. Salts of organic bases such as methyl, ethyl, or butyl amine; guanylurea, guanidine; hydroxyethylguanidine; biguanide; ethanolamine; triethanolamine; higher aliphatic amines; aromatic amines; heterocyclic bases such as nicotine, pyridine, quinoline; and alkaloids may also be prepared by the same method, as well as by direct sulfonation employing the sulfites and bisulfites of the organic bases.

Some of the advantages of the above composition and process of obtaining the composition are as follows.

The composition of this invention does not require that the unsaturation be reduced to below percent, nor require a low unsaturation" as would be evidenced by low iodine value; the ricinoleic acid content of the castor oil approaches about 87 percent (a high concentration) and the ricinoleic acid is highly unsaturated. Similarly the composition of this invention does not require a treatment to prevent the formation of insoluble resin; in contrast to the prior art processes, in the absence of such treatment, there is in the process of this invention no evidence of the formation of an insoluble resin. Moreover, the novel process of this invention of reacting to form the bis-ester of ricinoleic acid, for example, requires less strenuous reaction conditions, i.e., the reaction precedes more smoothly without difficulties at lower reaction temperatures and at shorter periods of time necessary to obtain the final product.

Additionally, the process of this invention has fewer required steps and is more economical In not requiring high reaction temperatures and long periods of time for reaction to take place. The process does not require the reduction" of unsaturationby hydrogenation. There are no difiiculties encountered as to any tendency to form insoluble resins during the process.

The softener composition of this invention is easily handled because it is a liquid", in contrast to the "solid" state of the prior art "tallow" product, for example. The softener composition of this invention is cold-water-soluble, in contrast to the tallow-product of prior art which requires hot water to obtain solubility. The softener composition of this invention imparts to a cellulosic or cellulosic-blend substrate the property of good rewettability, whereby it can be easily and quickly rewet. This is in contrast to the tallow-product, for example, which does not rewet easily nor quickly; good rewettability makes the novel composition of this invention of value for use on toweling, for example.

In employing the novel bis-esters of the invention in textile softening treatments, a dispersion of from about 0.5 percent to about 3 percent or more, based on the weight of the dispersion, of the selected bis-ester is prepared in aqueous medium or, if the textile is to be sized at the same time, in an aqueous size bath. The textile material is thereafter impregnated in the bath to a wet pickup of substantially percent of the weight of fabric and then dried according to normal operating procedure. Ordinarily, where no sizing agent is employed it is unnecessary to have more than about 1 percent of the softening agent on the fabric in order to obtain the desired softness of hand in the product. On the otherhand, where a sizing agent is used, it is sometimes necessary to increase the softening agent content to about 3 percent or more to obtain the desired improvement in softness of hand in the treated fabric.

The above-described invention is illustrated in the following example. The example, however, limits this invention only to the extent that such limitations appear in the appended claims.

EXAMPLE 1 One mole of castor oil (the triglyceride of mainly ricinoleic acid) is transesterified with two moles of glycerine in the presence of a trace of sodium hydroxide, using agitation and elevated temperatures. When this step is complete, xylene is added and the batch is cooled.

Fumaric acid (one-half mole of fumaric per mole of castor oil mixed glycerides) is added and the bis-ester of the castor oil mixed glycerides is formed, by stripping out water (azeotropic distillation).

The bis-ester is sulfonated at reflux, under pressure, in the presence of water, isopropyl alcohol, and sodium bisulfite (one mole sodium bisulfite per mole bis-ester).

It is understood that the above-described and illustrated invention is not limited except to the extent of the appended claims. It is within the scope of this invention to include substitutes and equivalences within the scope of the ordinary artisan.

I claim:

1. A metal salt of an ester of the formula:

BEST AVAILABLE COPY n, and n, is at least 1 to about 3.

2. A metal salt according to claim I, in which said cation is sodium.

tions, n and n are each integers from to 2, where the sum of m 3. A compound of the formula:

U S N 

2. A metal salt according to claim 1, in which said cation is sodium.
 3. A compound of the formula: 